技术领域technical field
本发明属于难降解有机废水的电化学处理技术领域，具体涉及用于高浓度有机废水处理的非均相电-Fenton装置。The invention belongs to the technical field of electrochemical treatment of refractory organic wastewater, and in particular relates to a heterogeneous electro-Fenton device for high-concentration organic wastewater treatment.
背景技术Background technique
电-Fenton法通过产生羟基自由基等强氧化性的活性基团来降解废水中的有机污染物，具有无二次污染、成本低、适用性强、效率高等特点，在处理高浓度、难生化降解废水方面具有应用潜力。为增强难生化降解废水的电-Fenton法处理效果，提高电解槽单位体积有效反应面积、传质效果和电流效率是非常关键的问题，因此需要开发新型高效的电-Fenton反应器。同时，将反应器的开发和与之相匹配的电极制备相结合进行，使电极的催化效率得到充分发挥是目前研究的重点之一。因此选择适合的电极材料和对其改性，以改善电极的表面催化性能，便成了电化学工作者研究的新课题。近30年来，钛基板电极已发展成为金属氧化物电极的主要形式，目前修饰钛电极所使用的金属氧化物主要有氧化钌、氧化锰、氧化铅、氧化铂、氧化铱、锡锑氧化物等。电催化电极的表面微观结构和状态是影响电催化性能的重要因素，而电极的制备方法直接影响到电极的表面结构，因而选择合适的电极制备方法是提高电极电催化活性至关重要的关键环节。目前还缺少将反应器的开发和与之相匹配的电极制备相结合方面的研究。The electro-Fenton method degrades organic pollutants in wastewater by generating strong oxidizing active groups such as hydroxyl radicals. It has the characteristics of no secondary pollution, low cost, strong applicability, and high efficiency. It has application potential in degrading wastewater. In order to enhance the treatment effect of the electro-Fenton method for refractory biodegradable wastewater, it is very important to improve the effective reaction area per unit volume of the electrolytic cell, the mass transfer effect and the current efficiency. Therefore, it is necessary to develop a new type of high-efficiency electro-Fenton reactor. At the same time, it is one of the focuses of current research to combine the development of the reactor with the matching electrode preparation so that the catalytic efficiency of the electrode can be fully utilized. Therefore, selecting suitable electrode materials and modifying them to improve the surface catalytic performance of electrodes has become a new research topic for electrochemists. In the past 30 years, titanium substrate electrodes have developed into the main form of metal oxide electrodes. At present, the metal oxides used to modify titanium electrodes mainly include ruthenium oxide, manganese oxide, lead oxide, platinum oxide, iridium oxide, tin antimony oxide, etc. . The surface microstructure and state of the electrocatalytic electrode are important factors affecting the electrocatalytic performance, and the preparation method of the electrode directly affects the surface structure of the electrode, so choosing a suitable electrode preparation method is a key link to improve the electrocatalytic activity of the electrode . There is still a lack of research on the combination of the development of the reactor and the preparation of the corresponding electrode.
发明内容Contents of the invention
本发明的目的是提供用于高浓度有机废水处理的非均相电-Fenton装置。本发明的具体内容如下：The object of the present invention is to provide a heterogeneous electro-Fenton device for the treatment of high-concentration organic wastewater. Concrete content of the present invention is as follows:
用于高浓度有机废水处理的非均相电-Fenton装置由电解槽(1)、电极插槽(2)、多金属复合阳极(3)、三维多孔阴极板(4)、颗粒活性炭(5)、挡板(6)、布气板(7)、进气管(8)、电线(9)、稳压稳流电源(10)、搅拌轴(11)、搅拌叶片(12)和搅拌电机(13)组成。在电解槽(1)的侧壁中下部开设进气管(8)的插孔；在电解槽(1)的底部安装布气板(7)，在布气板(7)上均匀开设孔径为1mm的布气孔，布气板(7)位于进气管(8)的上方；在布气板(7)的上方安装挡板(6)，在挡板(6)上均匀开设孔径为2mm的小孔；在电解槽(1)上共安装有4个电极插槽(2)，每两个插槽为一对，分别位于电解槽(1)的正面和对面壁上，插槽上均匀分布宽度为2mm的卡位，用于插入三维多孔阴极板(4)和多金属复合阳极(3)，卡位的间距为10mm；用电线(9)将三维多孔阴极板(4)和多金属复合阳极(3)与稳压稳流电源(10)相连；最后将颗粒活性炭(5)均匀投入三维多孔阴极板(4)和多金属复合阳极(3)之间的空隙中。搅拌叶片(12)分布在搅拌轴(11)的下端，搅拌轴(11)和搅拌电机(13)相连。The heterogeneous electro-Fenton device for the treatment of high-concentration organic wastewater consists of an electrolytic cell (1), an electrode socket (2), a multi-metal composite anode (3), a three-dimensional porous cathode plate (4), and granular activated carbon (5) . )composition. Open the jack of air inlet pipe (8) in the lower part of the side wall of electrolytic tank (1); Install gas distribution plate (7) at the bottom of electrolytic tank (1), and evenly set the hole diameter on the gas distribution plate (7) to be 1mm The air distribution hole, the air distribution plate (7) is located above the intake pipe (8); the baffle (6) is installed above the air distribution plate (7), and small holes with a diameter of 2mm are evenly opened on the baffle (6) ; 4 electrode slots (2) are installed on the electrolytic cell (1), and every two slots are a pair, which are respectively located on the front and the opposite wall of the electrolytic cell (1), and the uniform distribution width on the slot is The 2mm clamping position is used to insert the three-dimensional porous cathode plate (4) and the multi-metal composite anode (3), and the spacing between the clamping positions is 10mm; the three-dimensional porous cathode plate (4) and the multi-metal composite anode ( 3) Connected to a voltage-stabilized and current-stabilized power supply (10); finally, the granular activated carbon (5) is evenly put into the gap between the three-dimensional porous cathode plate (4) and the multi-metal composite anode (3). Stirring blades (12) are distributed on the lower end of the stirring shaft (11), and the stirring shaft (11) is connected with the stirring motor (13).
其中，所述三维多孔阴极板由如下方法制备：Wherein, the three-dimensional porous cathode plate is prepared by the following method:
(1)取7.5g活性炭粉加入500mL烧杯中，加入100mL去离子水并煮沸2h，除去上层杂质并真空抽滤，将抽滤后的活性炭粉放入90℃烘箱中干燥12h，得到物质A；(1) Take 7.5g of activated carbon powder and put it into a 500mL beaker, add 100mL of deionized water and boil for 2h, remove the upper impurities and vacuum filter, put the filtered activated carbon powder into a 90°C oven and dry for 12h to obtain substance A;
(2)将物质A放入500mL烧杯中，向烧杯中加入100mL浓度为0.55mol/L的HNO3，搅拌6h后放入90℃烘箱中干燥24h，得到物质B；(2) Put substance A into a 500mL beaker, add 100mL of HNO3 with a concentration of 0.55mol/L into the beaker, stir for 6 hours, then put it in an oven at 90°C for 24 hours to obtain substance B;
(3)将长度为60mm、宽度为40mm、厚度为2mm镍网放入1000mL烧杯中，加入700mL去离子水并煮沸1h，取出镍网用250mL去离子水清洗，将清洗后的镍网放入500mL烧杯中，加入100mL浓度为0.1mol/L的盐酸溶液浸泡0.5h，然后取出镍网用250mL去离子水冲洗，晾干后得到物质C；(3) Put the nickel mesh with a length of 60mm, a width of 40mm, and a thickness of 2mm into a 1000mL beaker, add 700mL of deionized water and boil for 1 hour, take out the nickel mesh and wash it with 250mL of deionized water, and put the cleaned nickel mesh into Into a 500mL beaker, add 100mL of hydrochloric acid solution with a concentration of 0.1mol/L and soak for 0.5h, then take out the nickel mesh and rinse it with 250mL of deionized water, dry it to obtain substance C;
(4)将5.5g物质B放入500mL烧杯中，然后加入10mL浓度为4.5mol/L的KNO3水溶液、9.0mL质量百分比浓度为28％的十二烷基酚聚氧乙烯醚水溶液、45mL乙醚、35mL甲醇，在100r/min条件下搅拌10min，然后加入8.5mL质量百分比浓度为75％的聚四氟乙烯乳液，在100r/min条件下搅拌10min，得到溶液A，将溶液A放入90℃恒温水浴锅中，至溶液呈膏状，得到膏状物A；(4) Put 5.5g of substance B into a 500mL beaker, then add 10mL of 4.5mol/LKNO3 aqueous solution, 9.0mL of 28% dodecylphenol polyoxyethylene ether aqueous solution, 45mL of diethyl ether , 35mL of methanol, stirred at 100r/min for 10min, then added 8.5mL of polytetrafluoroethylene emulsion with a mass percentage concentration of 75%, stirred at 100r/min for 10min to obtain solution A, and put solution A at 90°C In a constant temperature water bath, until the solution is in the form of a paste, the paste A is obtained;
(5)将膏状物A涂抹在物质C的一侧得到物质D，将物质D放于压片机上，在压力为2t条件下保压1min，得到物质E；(5) Apply paste A on one side of substance C to obtain substance D, put substance D on a tablet press, hold the pressure for 1min under the condition of a pressure of 2t, and obtain substance E;
(6)将3.00g十六烷基三甲基溴化铵、17.00mL正辛烷、5.00mL正丁醇依次加入250mL锥形瓶中，再加入2.00g偏钒酸铵和100mL去离子水，置于70℃水浴中在5000r/min条件下搅拌15min，得到微乳液B；(6) Add 3.00g of cetyltrimethylammonium bromide, 17.00mL of n-octane, and 5.00mL of n-butanol into a 250mL Erlenmeyer flask, then add 2.00g of ammonium metavanadate and 100mL of deionized water, Place in a 70°C water bath and stir for 15 minutes under the condition of 5000r/min to obtain microemulsion B;
(7)将3.00g十六烷基三甲基溴化铵、17.00mL正辛烷、5.00mL正丁醇依次加入250mL锥形瓶中，再加入100mL摩尔浓度为0.80mol/L的稀硫酸，在1000r/min条件下搅拌15min，得到微乳液C；(7) Add 3.00g of cetyltrimethylammonium bromide, 17.00mL of n-octane, and 5.00mL of n-butanol into a 250mL Erlenmeyer flask, and then add 100mL of dilute sulfuric acid with a molar concentration of 0.80mol/L, Stirring 15min under the condition of 1000r/min, obtain microemulsion C;
(8)将微乳液B与微乳液C混合，然后在1000r/min条件下搅拌10min，静置10h，再在6000r/min条件下离心20min，去除上清液，用15mL质量分数为95％的乙醇洗涤，重复洗涤5次，得到固体产物M；(8) Mix microemulsion B with microemulsion C, then stir for 10 min at 1000 r/min, let stand for 10 h, then centrifuge at 6000 r/min for 20 min, remove the supernatant, and use 15 mL of 95% Washing with ethanol, repeated washing 5 times, to obtain the solid product M;
(9)将固体产物M在100℃条件下干燥24h，再置于马弗炉中在500℃条件下焙烧2h，得到颗粒N；(9) drying the solid product M at 100°C for 24 hours, and then roasting it in a muffle furnace at 500°C for 2 hours to obtain particles N;
(10)将20mg颗粒N加入250mL锥形瓶中，再加入1.16g聚乙烯吡咯烷酮和100mL去离子水，超声震荡10min，加入1.00mL质量浓度为0.02g/mL的HAuCl4溶液，继续超声震荡5min；(10) Add 20mg of granule N into a 250mL Erlenmeyer flask, then add 1.16g of polyvinylpyrrolidone and 100mL of deionized water, ultrasonically oscillate for 10min, add 1.00mL of HAuCl4 solution with a mass concentration of 0.02g/mL, and continue to sonicate for 5min ;
(11)向步骤(10)处理后的锥形瓶中加入2.00mL重量百分比为1％的柠檬酸钠溶液，在40℃条件下震荡反应30min，在6000r/min条件下离心15min，去除上清液，然后用15mL去离子水洗涤，重复洗涤两遍，在20℃条件下干燥24h后获得固体产物P；(11) Add 2.00mL of 1% sodium citrate solution by weight to the Erlenmeyer flask treated in step (10), shake and react at 40°C for 30min, centrifuge at 6000r/min for 15min, and remove the supernatant liquid, then washed with 15 mL of deionized water, repeated washing twice, and dried at 20°C for 24 hours to obtain the solid product P;
(12)将5.00固体产物P、2.00g十二烷基苯磺酸钠、50mL去离子水加入150mL锥形瓶中，在1000r/min条件下搅拌10min，得到溶液D；(12) Add 5.00 g of solid product P, 2.00 g of sodium dodecylbenzenesulfonate, and 50 mL of deionized water into a 150 mL Erlenmeyer flask, and stir for 10 min at 1000 r/min to obtain solution D;
(13)将1.2g物质B放入500mL烧杯中，然后加入5.5mL浓度为4.5mol/L的KNO3水溶液、4.5mL质量百分比浓度为28％的十二烷基酚聚氧乙烯醚水溶液、45mL乙醚、35mL甲醇、5mL溶液D，在100r/min条件下搅拌10min，然后加入2.5mL质量百分比浓度为75％的聚四氟乙烯乳液，在100r/min条件下搅拌10min，得到溶液E，将溶液E放入80℃恒温水浴锅中，至溶液呈膏状，得到膏状物B；(13) Put 1.2g of substance B into a 500mL beaker, then add 5.5mL of 4.5mol/LKNO3 aqueous solution, 4.5mL of 28% dodecylphenol polyoxyethylene ether aqueous solution, 45mL Diethyl ether, 35mL methanol, and 5mL solution D were stirred at 100r/min for 10min, then 2.5mL of polytetrafluoroethylene emulsion with a concentration of 75% by mass was added, and stirred at 100r/min for 10min to obtain solution E. E is placed in a constant temperature water bath at 80°C until the solution is in the form of a paste to obtain a paste B;
(14)将膏状物B涂抹在物质E的另一侧得到物质F，将物质F放于压片机上，在压力为2t条件下保压1min，得到物质G；(14) Apply paste B on the other side of substance E to obtain substance F, put substance F on a tablet press, hold the pressure for 1min under the condition of a pressure of 2t, and obtain substance G;
(15)将物质G放入300℃马弗炉中煅烧1h，然后放在热压机中，在温度为350℃，压力为10t的条件下保压1min，冷却后即可得到三维多孔膜电极。(15) Put substance G in a muffle furnace at 300°C for calcination for 1 hour, then place it in a hot press, hold the pressure for 1 minute at a temperature of 350°C and a pressure of 10 t, and obtain a three-dimensional porous membrane electrode after cooling .
所述多金属复合阳极由如下方法制备：The multi-metal composite anode is prepared by the following method:
(1)用240号氧化铝耐水砂纸将钛片表面打磨至出现金属光泽，然后将其放入培养皿中，倒入50mL丙酮，在40kHz超声波清洗仪中用洗涤剂溶液清洗除油30min，取出先用自来水冲洗，再用去离子水冲洗，然后放置在40kHz超声波清洗仪中用去离子水清洗15min；(1) Use No. 240 alumina water-resistant sandpaper to polish the surface of the titanium sheet until it appears metallic luster, then put it into a petri dish, pour 50mL of acetone, clean and degrease with detergent solution in a 40kHz ultrasonic cleaner for 30min, and take out Rinse with tap water first, then rinse with deionized water, and then place it in a 40kHz ultrasonic cleaner for 15 minutes with deionized water;
(2)将步骤(1)得到的钛片放置在10％的草酸溶液中刻蚀2h，然后取出先用自来水冲洗，再用去离子水冲洗后放置在40kHz超声波仪器中用去离子水清洗15min，晾干后保存在无水乙醇中备用；(2) Place the titanium sheet obtained in step (1) in 10% oxalic acid solution to etch for 2 hours, then take it out and rinse it with tap water first, then rinse it with deionized water and place it in a 40kHz ultrasonic instrument for 15 minutes with deionized water , dried and stored in absolute ethanol for subsequent use;
(3)利用辉光放电对步骤(2)得到的钛片表面进行预处理10min，然后在MS56A型高真空多靶磁控溅射机上完成磁控溅射镀铂得到物质A，其中阴极靶材为铂片，钛片作为阳极基片，操作模式为射频溅射，真空度为8.0×10-2Pa，功率为100W，氩气压力为1pa；(3) Use glow discharge to pretreat the surface of the titanium sheet obtained in step (2) for 10 minutes, and then complete magnetron sputtering platinum plating on the MS56A high-vacuum multi-target magnetron sputtering machine to obtain substance A, wherein the cathode target Platinum sheet, titanium sheet as the anode substrate, the operation mode is radio frequency sputtering, the vacuum degree is 8.0×10-2 Pa, the power is 100W, and the argon gas pressure is 1pa;
(4)将正丁醇、异丙醇、异丁醇、无水乙醇按等体积比例混合，得到溶液A；将SnCl2.H2O溶于无水乙醇制成浓度为0.5mol/L的溶液B；将Zn(NO3)2.6H2O溶于无水乙醇制成浓度为0.5mol/L的溶液C1，另将Zn(NO3)2.6H2O溶于水中制成浓度为0.5mol/L的溶液并加入5滴硝酸以防水解，得到溶液C2；将Pb(NO3)2溶于水中制成浓度为0.5mol/L的溶液，加入5滴硝酸以防水解，得到溶液D；(4) Mix n-butanol, isopropanol, isobutanol, and dehydrated ethanol in an equal volume ratio to obtain solution A; dissolve SnCl2 .H2 O in dehydrated ethanol to make a solution with a concentration of 0.5mol/L Solution B: Dissolve Zn(NO3 )2 .6H2 O in absolute ethanol to make solution C1 with a concentration of 0.5mol/L, and dissolve Zn(NO3 )2 .6H2 O in water to make a concentration of 0.5mol/L solution and add 5 drops of nitric acid to prevent hydrolysis to obtain solution C2; dissolve Pb(NO3 )2 in water to make a solution with a concentration of 0.5mol/L, add 5 drops of nitric acid to prevent hydrolysis to obtain solution D;
(5)将溶液B与溶液C1按体积比2∶8混合，得到溶液E1；将溶液E1与溶液A等体积比混合，摇匀后分成等量3份，得到溶液F1-1、溶液F1-2、溶液F1-3；(5) Mix solution B and solution C1 at a volume ratio of 2:8 to obtain solution E1; mix solution E1 and solution A in an equal volume ratio, shake well and divide into 3 equal parts to obtain solution F1-1 and solution F1- 2. Solution F1-3;
(6)将溶液B与溶液C1按体积比4∶6混合，得到溶液E2；将溶液E2与溶液A等体积比混合，摇匀后分成等量3份，得到溶液F2-1、溶液F2-2、溶液F2-3；(6) Mix solution B and solution C1 at a volume ratio of 4:6 to obtain solution E2; mix solution E2 with solution A in an equal volume ratio, shake well and divide into 3 equal parts to obtain solution F2-1 and solution F2- 2. Solution F2-3;
(7)将溶液B与溶液C1按体积比6∶4混合，得到溶液E3；将溶液E3与溶液A等体积比混合，摇匀后分成等量3份，得到溶液F3-1、溶液F3-2、溶液F3-3；(7) Mix solution B and solution C1 at a volume ratio of 6:4 to obtain solution E3; mix solution E3 and solution A in an equal volume ratio, shake well and divide into 3 equal parts to obtain solution F3-1 and solution F3- 2. Solution F3-3;
(8)将溶液B与溶液C1按体积比8∶2混合，得到溶液E4；将溶液E4与溶液A等体积比混合，摇匀后分成等量3份，得到溶液F4-1、溶液F4-2、溶液F4-3；(8) Mix solution B and solution C1 at a volume ratio of 8:2 to obtain solution E4; mix solution E4 with solution A in an equal volume ratio, shake well and divide into 3 equal parts to obtain solution F4-1 and solution F4- 2. Solution F4-3;
(9)将溶液C2与溶液D按体积比3∶7混合，得到溶液G1；将溶液G1与溶液A等体积比混合，摇匀后分成等量2份，得到溶液H1-1、溶液H1-2；(9) Mix solution C2 and solution D at a volume ratio of 3:7 to obtain solution G1; mix solution G1 and solution A in an equal volume ratio, shake well and divide into 2 equal parts to obtain solution H1-1 and solution H1- 2;
(10)将溶液C2与溶液D按体积比1∶9混合，得到溶液G2；将溶液G2与溶液A等体积比混合，摇匀后分成等量2份，得到溶液H2-1、溶液H2-2；(10) Mix solution C2 and solution D at a volume ratio of 1:9 to obtain solution G2; mix solution G2 with solution A in an equal volume ratio, shake well and divide into 2 equal parts to obtain solution H2-1, solution H2- 2;
(11)将溶液D与溶液A等体积比混合，摇匀后分成等量4份，得到溶液D1、溶液D2、溶液D3、溶液D4；(11) Mix solution D and solution A in an equal volume ratio, shake well and divide into 4 equal parts to obtain solution D1, solution D2, solution D3, and solution D4;
(12)将步骤(3)得到的物质A浸入到溶液F1-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-1；(12) Immerse the substance A obtained in step (3) into the solution F1-1, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain substance B1-1 ;
(13)将物质B1-1浸入到溶液F2-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-1；(13) Immerse the substance B1-1 into the solution F2-1, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B2-1;
(14)将物质B2-1浸入到溶液F3-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-1；(14) Immerse the substance B2-1 into the solution F3-1, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B3-1;
(15)将物质B3-1浸入到溶液F4-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-1；(15) Immerse the substance B3-1 into the solution F4-1, and impregnate it uniformly under the action of a magnetic stirrer, take it out after 3 hours and dry it in the air, then dry it at 100°C for 10 hours, and place the dried substance in a muffle Calcined in a furnace at 600°C for 4 hours to obtain substance B4-1;
(16)将物质B4-1浸入到溶液F1-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-2；(16) Immerse the substance B4-1 into the solution F1-2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B1-2;
(17)将物质B1-2浸入到溶液F2-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-2；(17) Immerse the substance B1-2 into the solution F2-2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B2-2;
(18)将物质B2-2浸入到溶液F3-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-2；(18) Immerse the substance B2-2 into the solution F3-2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B3-2;
(19)将物质B3-2浸入到溶液F4-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-2；(19) Immerse the substance B3-2 into the solution F4-2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours, and place the dried substance in a muffle Calcined in a furnace at 600°C for 4 hours to obtain substance B4-2;
(20)将物质B4-2浸入到溶液F1-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-3；(20) Immerse the substance B4-2 into the solution F1-3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B1-3;
(21)将物质B1-3浸入到溶液F2-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-3；(21) Immerse the substance B1-3 into the solution F2-3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B2-3;
(22)将物质B2-3浸入到溶液F3-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-3；(22) Immerse the substance B2-3 into the solution F3-3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance B3-3;
(23)将物质B3-3浸入到溶液F4-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-3；(23) Immerse the substance B3-3 into the solution F4-3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours, and place the dried substance in a muffle Calcined in a furnace at 600°C for 4 hours to obtain substance B4-3;
(24)将物质B4-3浸入到溶液H1-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质C1-1；(24) Immerse the substance B4-3 into the solution H1-1, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance C1-1;
(25)将物质C1-1浸入到溶液H2-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质C2-1；(25) Immerse the substance C1-1 into the solution H2-1, and impregnate it uniformly under the action of a magnetic stirrer, take it out after 3 hours and dry it in the air, then dry it at 100°C for 10 hours, and place the dried substance in a muffle Roasting in a furnace at 600°C for 4 hours to obtain substance C2-1;
(26)将物质C2-1浸入到溶液H1-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质C1-2；(26) Immerse the substance C2-1 into the solution H1-2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance C1-2;
(27)将物质C1-2浸入到溶液H2-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质C2-2；(27) Immerse the substance C1-2 into the solution H2-2, and impregnate it uniformly under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours, and place the dried substance in a muffle Calcined in a furnace at 600°C for 4 hours to obtain substance C2-2;
(28)将物质C2-2浸入到溶液D1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质D1；(28) Immerse the substance C2-2 into the solution D1, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours to obtain the substance D1;
(29)将物质D1浸入到溶液D2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质D2；(29) Immerse the substance D1 into the solution D2, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours, put the dried substance in a muffle furnace at 600 Roasting at ℃ for 4h to obtain substance D2;
(30)将物质D2浸入到溶液D3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质D3；(30) Immerse the substance D2 into the solution D3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100° C. for 10 hours to obtain the substance D3;
(31)将物质D3浸入到溶液D4中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到的物质即为多金属复合阳极。(31) Immerse the substance D3 into the solution D4, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3 hours, and then dry it at 100°C for 10 hours, and place the dried substance in a muffle furnace at 600 Baking at ℃ for 4 hours, the obtained material is the multi-metal composite anode.
本发明的有益效果是，该非均相电-Fenton装置对含多种难降解有机化合物废水处理效率高、成本低、操作简单。The beneficial effect of the invention is that the heterogeneous electro-Fenton device has high treatment efficiency for wastewater containing various refractory organic compounds, low cost and simple operation.
附图说明Description of drawings
附图1是非均相电-Fenton装置的透视图。附图1中1为电解槽，2为电极插槽，3为多金属复合阳极，4为三维多孔阴极板，5为颗粒活性炭，6为挡板，7为布气板，8为进气管，9为电线，10为稳压稳流电源，11为搅拌轴、12为搅拌叶片、13为搅拌电机。Figure 1 is a perspective view of a heterogeneous electro-Fenton device. In accompanying drawing 1, 1 is an electrolytic cell, 2 is an electrode slot, 3 is a multi-metal composite anode, 4 is a three-dimensional porous cathode plate, 5 is granular activated carbon, 6 is a baffle plate, 7 is an air distribution plate, and 8 is an air intake pipe. 9 is an electric wire, 10 is a voltage-stabilizing power supply, 11 is a stirring shaft, 12 is a stirring blade, and 13 is a stirring motor.
具体实施方式Detailed ways
实施例Example
(1)用于高浓度有机废水处理的非均相电-Fenton装置的制备过程如下：(1) The preparation process of the heterogeneous electro-Fenton device for the treatment of high-concentration organic wastewater is as follows:
电解槽的长为60mm，宽为50mm，高为120mm。在电解槽侧壁中心线上距底部10mm处开设孔径为2mm的进气管插孔。布气板是长为56mm、宽为46mm、厚为3mm的薄板，在布气板上均匀开设孔径为1mm的布气孔，布气板距电解槽底部的距离为15mm。挡板是长为56mm、宽为46mm、厚为5mm的薄板，在挡板上均匀开设孔径为2mm的小孔，挡板距电解槽底部的距离为20mm。共有4个电极插槽，每两个插槽为一对，分别位于电解槽的正面和对面壁上，下面的插槽距电解槽底部的距离为35mm，上面的插槽距电解槽底部的距离为85mm，每个插槽上均匀分布宽度为2mm的卡位，卡位的间距为10mm，用于插入长度为60mm、宽度为40mm、厚度为2mm的三维多孔阴极板和多金属复合阳极。用电线将三维多孔阴极板和多金属复合阳极与稳压稳流电源相连。最后将颗粒活性炭均匀投入三维多孔阴极板和多金属复合阳极之间的空隙中。在搅拌轴的下端安装搅拌叶片，最后连接搅拌电机。The length of the electrolytic cell is 60mm, the width is 50mm, and the height is 120mm. On the center line of the side wall of the electrolytic cell, an inlet pipe jack with a diameter of 2 mm is opened at a distance of 10 mm from the bottom. The air distribution plate is a thin plate with a length of 56mm, a width of 46mm, and a thickness of 3mm. Air distribution holes with a diameter of 1mm are evenly opened on the air distribution plate. The distance between the air distribution plate and the bottom of the electrolytic cell is 15mm. The baffle plate is a thin plate with a length of 56 mm, a width of 46 mm, and a thickness of 5 mm. Small holes with a diameter of 2 mm are evenly opened on the baffle plate, and the distance between the baffle plate and the bottom of the electrolytic cell is 20 mm. There are 4 electrode slots in total, each pair of two slots are located on the front and opposite walls of the electrolytic cell respectively, the distance between the lower slot and the bottom of the electrolytic cell is 35mm, and the distance between the upper slot and the bottom of the electrolytic cell 85mm, each slot is evenly distributed with a width of 2mm, and the distance between the card positions is 10mm, which is used to insert a three-dimensional porous cathode plate and a multi-metal composite anode with a length of 60mm, a width of 40mm, and a thickness of 2mm. The three-dimensional porous cathode plate and the multi-metal composite anode are connected with a stable voltage and current power supply by wires. Finally, the granular activated carbon is evenly put into the gap between the three-dimensional porous cathode plate and the multi-metal composite anode. A stirring blade is installed at the lower end of the stirring shaft, and finally a stirring motor is connected.
(2)三维多孔阴极板由如下方法制备：(2) The three-dimensional porous cathode plate is prepared by the following method:
取7.5g活性炭粉加入500mL烧杯中，加入100mL去离子水并煮沸2h，除去上层杂质并真空抽滤，将抽滤后的活性炭粉放入90℃烘箱中干燥12h，得到物质A；将物质A放入500mL烧杯中，向烧杯中加入100mL浓度为0.55mol/L的HNO3，搅拌6h后放入90℃烘箱中干燥24h，得到物质B；Take 7.5g of activated carbon powder and put it into a 500mL beaker, add 100mL of deionized water and boil for 2h, remove the upper impurities and vacuum filter, put the filtered activated carbon powder in a 90°C oven and dry for 12h to obtain substance A; Put it into a 500mL beaker, add 100mL of HNO3 with a concentration of 0.55mol/L into the beaker, stir for 6h, put it in an oven at 90°C for 24h, and obtain substance B;
将长度为60mm、宽度为40mm、厚度为2mm镍网放入1000mL烧杯中，加入700mL去离子水并煮沸1h，取出镍网用250mL去离子水清洗，将清洗后的镍网放入500mL烧杯中，加入100mL浓度为0.1mol/L的盐酸溶液浸泡0.5h，然后取出镍网用250mL去离子水冲洗，晾干后得到物质C；Put the nickel mesh with a length of 60mm, a width of 40mm, and a thickness of 2mm into a 1000mL beaker, add 700mL of deionized water and boil for 1h, take out the nickel mesh and wash it with 250mL of deionized water, and put the cleaned nickel mesh into a 500mL beaker , add 100mL of hydrochloric acid solution with a concentration of 0.1mol/L and soak for 0.5h, then take out the nickel mesh and wash it with 250mL of deionized water, and obtain substance C after drying;
将5.5g物质B放入500mL烧杯中，然后加入10mL浓度为4.5mol/L的KNO3水溶液、9.0mL质量百分比浓度为28％的十二烷基酚聚氧乙烯醚水溶液、45mL乙醚、35mL甲醇，在100r/min条件下搅拌10min，然后加入8.5mL质量百分比浓度为75％的聚四氟乙烯乳液，在100r/min条件下搅拌10min，得到溶液A，将溶液A放入90℃恒温水浴锅中，至溶液呈膏状，得到膏状物A；Put 5.5g of substance B into a 500mL beaker, then add 10mL of 4.5mol/LKNO3 aqueous solution, 9.0mL of 28% dodecylphenol polyoxyethylene ether aqueous solution, 45mL of ether, 35mL of methanol , stirred at 100r/min for 10min, then added 8.5mL polytetrafluoroethylene emulsion with a mass percentage concentration of 75%, stirred at 100r/min for 10min to obtain solution A, and put solution A into a 90°C constant temperature water bath In, until the solution is paste-like, paste A is obtained;
将膏状物A涂抹在物质C的一侧得到物质D，将物质D放于压片机上，在压力为2t条件下保压1min，得到物质E；Apply the paste A on one side of the substance C to obtain the substance D, put the substance D on the tablet press, hold the pressure for 1min under the condition of a pressure of 2t, and obtain the substance E;
将3.00g十六烷基三甲基溴化铵、17.00mL正辛烷、5.00mL正丁醇依次加入250mL锥形瓶中，再加入2.00g偏钒酸铵和100mL去离子水，置于70℃水浴中在5000r/min条件下搅拌15min，得到微乳液B；Add 3.00g of cetyltrimethylammonium bromide, 17.00mL of n-octane, and 5.00mL of n-butanol into a 250mL Erlenmeyer flask, then add 2.00g of ammonium metavanadate and 100mL of deionized water, and place at 70 Stir in a water bath at 5000r/min for 15min to obtain microemulsion B;
将3.00g十六烷基三甲基溴化铵、17.00mL正辛烷、5.00mL正丁醇依次加入250mL锥形瓶中，再加入100mL摩尔浓度为0.80mol/L的稀硫酸，在1000r/min条件下搅拌15min，得到微乳液C；Add 3.00g of cetyltrimethylammonium bromide, 17.00mL of n-octane, and 5.00mL of n-butanol into a 250mL Erlenmeyer flask in sequence, then add 100mL of dilute sulfuric acid with a molar concentration of 0.80mol/L, at 1000r/ Stirring for 15min under min condition, obtain microemulsion C;
将微乳液B与微乳液C混合，然后在1000r/min条件下搅拌10min，静置10h，再在6000r/min条件下离心20min，去除上清液，用15mL质量分数为95％的乙醇洗涤，重复洗涤5次，得到固体产物M；Mix microemulsion B and microemulsion C, then stir at 1000r/min for 10min, let stand for 10h, then centrifuge at 6000r/min for 20min, remove the supernatant, wash with 15mL of ethanol with a mass fraction of 95%, Repeat washing 5 times to obtain solid product M;
将固体产物M在100℃条件下干燥24h，再置于马弗炉中在500℃条件下焙烧2h，得到颗粒N；将20mg颗粒N加入250mL锥形瓶中，再加入1.16g聚乙烯吡咯烷酮和100mL去离子水，超声震荡10min，加入1.00mL质量浓度为0.02g/mL的HAuCl4溶液，继续超声震荡5min；向锥形瓶中加入2.00mL重量百分比为1％的柠檬酸钠溶液，在40℃条件下震荡反应30min，在6000r/min条件下离心15min，去除上清液，然后用15mL去离子水洗涤，重复洗涤两遍，在20℃条件下干燥24h后获得固体产物P；The solid product M was dried at 100°C for 24 hours, then placed in a muffle furnace and roasted at 500°C for 2 hours to obtain particle N; 20mg of particle N was added to a 250mL Erlenmeyer flask, and then 1.16g of polyvinylpyrrolidone and 100mL deionized water, ultrasonic vibration for 10min, add1.00mL of HAuCl4 solution with a mass concentration of 0.02g/mL, continue ultrasonic vibration for 5min; add 2.00mL of 1% by weight sodium citrate solution to the Shake the reaction at ℃ for 30 minutes, centrifuge at 6000r/min for 15 minutes, remove the supernatant, then wash with 15mL deionized water, repeat the washing twice, and dry at 20℃ for 24h to obtain the solid product P;
将5.00固体产物P、2.00g十二烷基苯磺酸钠、50mL去离子水加入150mL锥形瓶中，在1000r/min条件下搅拌10min，得到溶液D；Add 5.00 g of solid product P, 2.00 g of sodium dodecylbenzenesulfonate, and 50 mL of deionized water into a 150 mL Erlenmeyer flask, and stir at 1000 r/min for 10 min to obtain solution D;
将1.2g物质B放入500mL烧杯中，然后加入5.5mL浓度为4.5mol/L的KNO3水溶液、4.5mL质量百分比浓度为28％的十二烷基酚聚氧乙烯醚水溶液、45mL乙醚、35mL甲醇、5mL溶液D，在100r/min条件下搅拌10min，然后加入2.5mL质量百分比浓度为75％的聚四氟乙烯乳液，在100r/min条件下搅拌10min，得到溶液E，将溶液E放入80℃恒温水浴锅中，至溶液呈膏状，得到膏状物B；Put 1.2g of substance B into a 500mL beaker, then add 5.5mL of 4.5mol/LKNO3 aqueous solution, 4.5mL of 28% dodecylphenol polyoxyethylene ether aqueous solution, 45mL of diethyl ether, 35mL Methanol, 5mL solution D, stirred at 100r/min for 10min, then added 2.5mL polytetrafluoroethylene emulsion with a mass percent concentration of 75%, stirred at 100r/min for 10min to obtain solution E, put solution E into In a constant temperature water bath at 80°C, until the solution is in the form of a paste, the paste B is obtained;
将膏状物B涂抹在物质E的另一侧得到物质F，将物质F放于压片机上，在压力为2t条件下保压1min，得到物质G；Apply paste B on the other side of substance E to obtain substance F, put substance F on a tablet press, hold the pressure for 1min under the condition of a pressure of 2t, and obtain substance G;
将物质G放入300℃马弗炉中煅烧1h，然后放在热压机中，在温度为350℃，压力为10t的条件下保压1min，冷却后即可得到三维多孔膜电极。Substance G was calcined in a muffle furnace at 300 °C for 1 h, then placed in a hot press, kept at a temperature of 350 °C and a pressure of 10 t for 1 min, and cooled to obtain a three-dimensional porous membrane electrode.
(3)多金属复合阳极由如下过程制备：(3) The multi-metal composite anode is prepared by the following process:
将长度为60mm、宽度为40mm、厚度为2mm的钛片用240号氧化铝耐水砂纸打磨至表面出现金属光泽，然后将其放入培养皿中，倒入50mL丙酮，在40kHz超声波清洗仪中用洗涤剂溶液清洗除油30min，然后取出先用500mL自来水冲洗，再用100mL去离子水冲洗，再放置在40kHz超声波清洗仪中用去离子水清洗15min；然后将清洗后的钛片放置在100mL质量浓度为10％的草酸溶液中刻蚀2h，取出先用500mL自来水冲洗，再用100mL去离子水冲洗，再放置在40kHz超声波仪器中用去离子水清洗15min，晾干后保存在无水乙醇中备用；Polish a titanium sheet with a length of 60 mm, a width of 40 mm, and a thickness of 2 mm with 240-grade alumina water-resistant sandpaper until the surface appears metallic luster, then put it into a petri dish, pour 50 mL of acetone, and use it in a 40 kHz ultrasonic cleaner. Wash and degrease with detergent solution for 30 minutes, then take it out and rinse it with 500mL tap water, then rinse it with 100mL deionized water, and then place it in a 40kHz ultrasonic cleaner and clean it with deionized water for 15min; then place the cleaned titanium sheet in a 100mL mass Etch in 10% oxalic acid solution for 2 hours, take it out and rinse it with 500mL tap water, then rinse it with 100mL deionized water, then place it in a 40kHz ultrasonic instrument and wash it with deionized water for 15min, dry it and store it in absolute ethanol spare;
取出保存在无水乙醇中的钛片，利用辉光放电对其表面进行预处理10min，然后在MS56A型高真空多靶磁控溅射机上完成磁控溅射镀铂得到物质A，其中阴极靶材为铂片，钛片作为阳极基片，操作模式为射频溅射，真空度为8.0×10-2Pa，功率为100W，氩气压力为1pa；The titanium sheet stored in absolute ethanol was taken out, and the surface was pretreated for 10 minutes by glow discharge, and then magnetron sputtering platinum plating was completed on the MS56A high-vacuum multi-target magnetron sputtering machine to obtain substance A, in which the cathode target The material is platinum sheet, the titanium sheet is used as the anode substrate, the operation mode is radio frequency sputtering, the vacuum degree is 8.0×10-2 Pa, the power is 100W, and the argon gas pressure is 1pa;
将150mL正丁醇、150mL异丙醇、150mL异丁醇和150mL无水乙醇混合均匀，得到600mL溶液A；将20.8克SnCl2.H2O溶于200mL无水乙醇制成浓度为0.5mol/L的溶液B；将29.7克Zn(NO3)2.6H2O溶于200mL无水乙醇中制成浓度为0.5mol/L的溶液C1，将29.7克Zn(NO3)2.6H2O溶于200mL水中制成浓度为0.5mol/L的溶液，加入5滴硝酸以防水解，得到200mL溶液C2；将33.1克Pb(NO3)2溶于200mL水中制成浓度为0.5mol/L的溶液，加入5滴硝酸以防水解，得到溶液D；Mix 150mL of n-butanol, 150mL of isopropanol, 150mL of isobutanol and 150mL of absolute ethanol to obtain 600mL of solution A; dissolve 20.8g of SnCl2 .H2 O in 200mL of absolute ethanol to make a concentration of 0.5mol/L solution B; 29.7 grams of Zn(NO3 )2 .6H2 O was dissolved in 200 mL of absolute ethanol to make solution C1 with a concentration of 0.5 mol/L, and 29.7 grams of Zn(NO3 )2 .6H2 O was dissolved in Make a solution with a concentration of 0.5mol/L in 200mL water, add 5 drops of nitric acid to prevent hydrolysis, and obtain 200mL solution C2; dissolve 33.1 grams of Pb(NO3 )2 in 200mL water to make a solution with a concentration of 0.5mol/L , adding 5 drops of nitric acid to prevent hydrolysis to obtain solution D;
将15mL溶液B与60mL溶液C1混合，得到75mL溶液E1；将75mL溶液E1与75mL溶液A混合，摇匀后分成等量3份，得到50mL溶液F1-1、50mL溶液F1-2、50mL溶液F1-3；Mix 15mL solution B with 60mL solution C1 to obtain 75mL solution E1; mix 75mL solution E1 with 75mL solution A, shake well and divide into 3 equal parts to obtain 50mL solution F1-1, 50mL solution F1-2, 50mL solution F1 -3;
将30mL溶液B与45mL溶液C1混合，得到75mL溶液E2；将75mL溶液E2与75mL溶液A混合，摇匀后分成等量3份，得到50mL溶液F2-1、50mL溶液F2-2、50mL溶液F2-3；Mix 30mL solution B with 45mL solution C1 to obtain 75mL solution E2; mix 75mL solution E2 with 75mL solution A, shake well and divide into 3 equal parts to obtain 50mL solution F2-1, 50mL solution F2-2, 50mL solution F2 -3;
将45mL溶液B与30mL溶液C1混合，得到75mL溶液E3；将75mL溶液E3与75mL溶液A混合，摇匀后分成等量3份，得到50mL溶液F3-1、50mL溶液F3-2、50mL溶液F3-3；Mix 45mL solution B with 30mL solution C1 to obtain 75mL solution E3; mix 75mL solution E3 with 75mL solution A, shake well and divide into 3 equal parts to obtain 50mL solution F3-1, 50mL solution F3-2, 50mL solution F3 -3;
将60mL溶液B与15mL溶液C1混合，得到75mL溶液E4；将75mL溶液E4与75mL溶液A混合，摇匀后分成等量3份，得到50mL溶液F4-1、50mL溶液F4-2、50mL溶液F4-3；Mix 60mL solution B with 15mL solution C1 to obtain 75mL solution E4; mix 75mL solution E4 with 75mL solution A, shake well and divide into 3 equal parts to obtain 50mL solution F4-1, 50mL solution F4-2, 50mL solution F4 -3;
将15mL溶液C2与35mL溶液D混合，得到50mL溶液G1；将50mL溶液G1与50mL溶液A混合，摇匀后分成等量2份，得到50mL溶液H1-1、50mL溶液H1-2；Mix 15mL of solution C2 with 35mL of solution D to obtain 50mL of solution G1; mix 50mL of solution G1 with 50mL of solution A, shake well and divide into 2 equal parts to obtain 50mL of solution H1-1 and 50mL of solution H1-2;
将5mL溶液C2与45mL溶液D混合，得到50mL溶液G2；将50mL溶液G2与50mL溶液A混合，摇匀后分成等量2份，得到50mL溶液H2-1、50mL溶液H2-2；Mix 5mL of solution C2 with 45mL of solution D to obtain 50mL of solution G2; mix 50mL of solution G2 with 50mL of solution A, shake well and divide into 2 equal parts to obtain 50mL of solution H2-1 and 50mL of solution H2-2;
将100mL溶液D与100mL溶液A等体积比混合，摇匀后分成等量4份，得到50mL溶液D1、50mL溶液D2、50mL溶液D3、50mL溶液D4；Mix 100mL solution D and 100mL solution A in an equal volume ratio, shake well and divide into 4 equal parts to obtain 50mL solution D1, 50mL solution D2, 50mL solution D3, and 50mL solution D4;
将物质A浸入到50mL溶液F1-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-1；Immerse substance A into 50mL solution F1-1, and impregnate evenly under the action of a magnetic stirrer, take it out to dry after 3h, and then dry at 100°C for 10h to obtain substance B1-1;
将物质B1-1浸入到50mL溶液F2-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-1；Substance B1-1 was immersed in 50mL solution F2-1, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance B2-1;
将物质B2-1浸入到50mL溶液F3-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-1；Substance B2-1 was immersed in 50mL of solution F3-1, and evenly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance B3-1;
将物质B3-1浸入到50mL溶液F4-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-1；Immerse substance B3-1 into 50mL solution F4-1, and impregnate evenly under the action of a magnetic stirrer, take it out after 3h to dry, then dry at 100°C for 10h, and place the dried substance in a muffle furnace Calcined at 600°C for 4 hours to obtain substance B4-1;
将物质B4-1浸入到50mL溶液F1-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-2；Substance B4-1 was immersed in 50mL of solution F1-2, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance B1-2;
将物质B1-2浸入到50mL溶液F2-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-2；Substance B1-2 was immersed in 50mL solution F2-2, and evenly impregnated under the action of a magnetic stirrer, taken out to dry after 3h, and then dried at 100°C for 10h to obtain substance B2-2;
将物质B2-2浸入到50mL溶液F3-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-2；Substance B2-2 was immersed in 50mL solution F3-2, and evenly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance B3-2;
将物质B3-2浸入到50mL溶液F4-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-2；Immerse substance B3-2 into 50mL solution F4-2, and impregnate evenly under the action of a magnetic stirrer, take it out after 3h and dry it in the air, then dry it at 100°C for 10h, and place the dried substance in a muffle furnace Calcined at 600°C for 4 hours to obtain substance B4-2;
将物质B4-2浸入到50mL溶液F1-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B1-3；Substance B4-2 was immersed in 50mL solution F1-3, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3h, and then dried at 100°C for 10h to obtain substance B1-3;
将物质B1-3浸入到50mL溶液F2-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B2-3；Substance B1-3 was immersed in 50mL solution F2-3, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3h, and then dried at 100°C for 10h to obtain substance B2-3;
将物质B2-3浸入到50mL溶液F3-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质B3-3；Substance B2-3 was immersed in 50mL solution F3-3, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance B3-3;
将物质B3-3浸入到50mL溶液F4-3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质B4-3；Immerse substance B3-3 into 50mL solution F4-3, and impregnate evenly under the action of a magnetic stirrer, take it out after 3h and dry it in the air, then dry it at 100°C for 10h, and place the dried substance in a muffle furnace Calcined at 600°C for 4 hours to obtain substance B4-3;
将物质B4-3浸入到50mL溶液H1-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质C1-1；Substance B4-3 was immersed in 50mL of solution H1-1, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance C1-1;
将物质C1-1浸入到50mL溶液H2-1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质C2-1；Immerse substance C1-1 into 50mL solution H2-1, and impregnate evenly under the action of a magnetic stirrer, take it out after 3h and dry it in the air, then dry it at 100°C for 10h, and place the dried substance in a muffle furnace Calcined at 600°C for 4 hours to obtain substance C2-1;
将物质C2-1浸入到50mL溶液H1-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质C1-2；Substance C2-1 was immersed in 50mL of solution H1-2, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance C1-2;
将物质C1-2浸入到50mL溶液H2-2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质C2-2；Immerse substance C1-2 into 50mL solution H2-2, and impregnate evenly under the action of a magnetic stirrer, take it out after 3h and dry it in the air, then dry it at 100°C for 10h, and place the dried substance in a muffle furnace Calcined at 600°C for 4 hours to obtain substance C2-2;
将物质C2-2浸入到50mL溶液D1中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质D1；Substance C2-2 was immersed in 50mL of solution D1, and uniformly impregnated under the action of a magnetic stirrer, taken out to dry after 3 hours, and then dried at 100°C for 10 hours to obtain substance D1;
将物质D1浸入到50mL溶液D2中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到物质D2；Immerse substance D1 into 50mL solution D2, and impregnate evenly under the action of a magnetic stirrer, take it out to dry after 3h, then dry at 100°C for 10h, put the dried substance in a muffle furnace at 600°C Lower roasting 4h, obtains substance D2;
将物质D2浸入到50mL溶液D3中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，得到物质D3；Immerse the substance D2 into 50mL solution D3, and uniformly impregnate it under the action of a magnetic stirrer, take it out to dry after 3h, and then dry it at 100°C for 10h to obtain the substance D3;
将物质D3浸入到50mL溶液D4中，并在磁力搅拌器作用下均匀浸渍，3h后取出晾干，然后在100℃条件下干燥10h，将干燥后的物质置于马弗炉中在600℃条件下焙烧4h，得到的物质即为多金属复合阳极。Immerse substance D3 into 50mL solution D4, and impregnate evenly under the action of a magnetic stirrer, take it out to dry after 3h, then dry at 100°C for 10h, put the dried substance in a muffle furnace at 600°C The material obtained is the multi-metal composite anode after being calcined for 4 hours.
(4)降解实验(4) Degradation experiment
运用本发明得到的非均相电-Fenton装置对含多种难降解有机化合物废水进行了降解试验，结果表明该非均相电-Fenton装置能够高效去除废水中的多种难降解有机化合物，当进水COD为697mg/L时，处理后出水中的COD降低到42mg/L。Using the heterogeneous electro-Fenton device obtained by the present invention to carry out degradation tests on wastewater containing various refractory organic compounds, the results show that the heterogeneous electro-Fenton device can efficiently remove various refractory organic compounds in wastewater, when When the influent COD is 697mg/L, the COD in the effluent after treatment is reduced to 42mg/L.
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